Process for producing hydrocarbons

ABSTRACT

A process for producing hydrocarbons which comprises bringing a gas mixture comprising hydrogen and carbon monoxide into contact with a catalyst comprising manganese oxide, alkali metal, sulfur, and ruthenium to produce hydrocarbons. The hydrocarbons formed are rich in olefins. When a catalyst prepared by combining the above described catalyst with crystalline zeolite is used, the hydrocarbons formed becomes rich in liquid hydrocarbons, particularly, a gasoline fraction.

This is a continuation of application Ser. No. 784,084 filed Oct. 4,1985 which is now abandoned.

FIELD OF THE INVENTION

The present invention relates to a process for effectively producinghydrocarbons, particularly those rich in olefinic hydrocarbons andliquid hydrocarbons, from a gas mixture composed of hydrogen and carbonmonoxide (hereinafter, referred to as synthesis gas).

BACKGROUND OF THE INVENTION

It is known to produce hydrocarbons by bringing a gas mixture composedof hydrogen and carbon monoxide into contact with a catalyst at anelevated temperature under pressure, as the synthesis of hydrocarbons bythe so-called Fischer-Tropsch (FT) process.

The catalytic hydrogenation of carbon monoxide yields a mixture composedof paraffins and olefins having from 1 to 40 carbon atoms, dependingupon the catalyst used, and the reaction conditions applied, and itsometimes yields compounds containing oxygen such as alcohol, aldehyde,ketone, ester, or aliphatic acid. Further, under specific syntheticconditions, a small amount of aromatic hydrocarbons is formed.

Remarkable activity for hydrogenation of carbon monoxide is shown byPeriodic Group VIII elements, particularly, iron, cobalt, nickel andruthenium. Even though these elements are used, distributions of theproducts and compositions thereof vary remarkably, depending upon thekind and the amounts of the elements. It is already known that nickel,cobalt, and ruthenium type catalysts produce mainly a mixture ofunbranched saturated hydrocarbons, and that hydrocarbons containingunsaturated aliphatic compounds and oxygen-containing compounds,particularly aliphatic primary alcohols, can be produced using aniron-containing catalyst.

However, the iron type catalysts produce a mixed product rich inunsaturated hydrocarbons, but amounts of carbon dioxide gas andoxygen-containing compounds formed as by-products are large, andselectivity of hydrocarbons is inferior. On the other hand, theruthenium type catalysts have a high FT reaction activity which isseveral times higher than that of the iron type catalysts, but theyproduce a product having a larger amount of saturated hydrocarbons, andhave high dependence on the reaction pressure and reaction temperature,and there is a tendency that the chain growth probability: α value ofSchultz-Flory law, which is often used as an index of FT reaction,greatly decreases with increases of the reaction temperature. For such areason, it has been said that it is very difficult to selectivelyproduce a reaction product containing a large amount of olefinichydrocarbons using the ruthenium type catalyst. Further, since the irontype catalysts used in the known processes have low reaction activity,iron content per unit catalyst is large, and the reaction is carried outat a high temperature. Carbon monoxide forms carbon at a high reactiontemperature according to Boudouard's equilibrium. Deposition of thecarbon causes deactivation of the catalyst and destruction of thecatalyst structure; consequently, the catalyst life is remarkablyreduced. Further, since the iron content is high, there is a problem inthat a sintering phenomenon occurs to a significant extent, and theuseful life of the catalyst is unsatisfactory.

Catalysts for hydrogenating carbon monoxide ordinary used are sensitiveto poisoning, most particularly with respect to sulfur compounds.Therefore, it is necessary to purify the raw materials of carbonmonoxide and hydrogen, and thus it is urgently required to develop asulfur resisting catalyst considering economy of the process. Further,in the case of producing olefins by hydrogenating carbon monoxide,though a higher conversion can be attained with increase of hydrogenpartial pressure, hydrogenation of the olefins formed is accelerated atthe same time, to result in deterioration of olefin selectivity for theproduct. Moreover, it is more difficult to increase the production ratioof ethylene/ethane than to increase the production ratio ofpropylene/propane, in the viewpoint of equilibrium in the FT reaction.

In recent years, a conversion process for selectively obtaining liquidhydrocarbons, and particularly a gasoline fraction from a synthesis gas,which comprises using zeolite and a carbon monoxide reduction catalyst(FT synthetic catalyst and methanol synthetic catalyst) in combinationhas been studied.

This conversion process includes a two-stage conversion process whereinthe reactions are carried out in different reactors, and a one-stageprocess wherein a catalyst comprising a metal component active toreduction of carbon monoxide supported on specified zeolite is used or amixed catalyst which is a physical mixture of a carbon monoxidereduction catalyst and a specified zeolite is used.

The one-stage process is generally expected to be a more economicprocess than the two-stage process, because the process is simplified.However, satisfactory results in reaction activity or distribution orcomposition of the formed hydrocarbon product are not obtained in theone-stage process, because the optimum conditions (particularly,reaction temperature and pressure) for the two catalysts are differentfrom each other, as compared with the two-stage process wherein thecarbon monoxide reduction catalyst and the zeolite catalyst can be usedunder the optimum conditions, respectively. For example, processes forselectively producing a gasoline fraction in one stage using aruthenium-containing catalyst of this kind are known in U.S. Pat. No.4,157,338 and Japanese Patent Application (OPI) Nos. 19386/83,127784/83, and 192834/83 (the term "OPI" as used herein refers to a"published unexamined Japanese Patent Application open to publicinspection"). However, these processes have disadvantages in that theamount of methane formed is large and yield of the gasoline fraction islow, conversion of carbon monoxide is low and/or high reaction pressureis required.

As is described above, it is very difficult to selectively producehydrocarbons of the specified useful component or the specified gasolinefraction by the prior processes, because undesirable methane or carbondioxide gas is formed in a relatively large amount as the by-product,selectivity for the desired hydrocarbons is low, and carbon atomdistribution of the formed hydrocarbons is very broad and hydrocarbonsin a range of gas to wax are formed.

SUMMARY OF THE INVENTION

It has now been found that ruthenium type carbon monoxide reductioncatalysts containing alkali metal and sulfur together with manganeseoxide show unique behavior in that they have excellent performance inthe formation of hydrocarbons rich in olefin in a contact reaction(carbon monoxide reduction reaction) between carbon monoxide andhydrogen. Furthermore, when this carbon monoxide reduction catalyst iscombined with zeolite, it shows an excellent performance in convertingthe reaction product rich in olefin into liquid hydrocarbons,particularly hydrocarbons rich in the gasoline fraction. Thus, thepresent invention have been completed. The excellent performances of thecatalysts used in the present invention in production of the specifiedhydrocarbon components is believed to be based on the oxidation numberor crystal structure of the manganese oxide composing the catalyst asdescribed later in examples and comparative examples, and, at the sametime, based on the coexistence of the alkali metal and the sulfurcomponent contained together therewith.

One object of the present invention is to provide a process forproducing hydrocarbons, particularly hydrocarbons rich in olefinichydrocarbons or liquid hydrocarbons in good selectivity.

Another object is to provide a process for producing the desiredhydrocarbons in good selectivity while preventing formation of methane.

A further object is to provide a process for producing the desiredhydrocarbons in good conversion.

Accordingly, the present invention is a process for producinghydrocarbons which comprises bringing a gas mixture comprising hydrogenand carbon monoxide into contact with a catalyst comprising manganeseoxide, alkali metal, sulfur, and ruthenium to produce hydrocarbons.

DETAILED DESCRIPTION OF THE INVENTION

The catalysts used in the present invention are those wherein rutheniumis supported on manganese oxide, and alkali metal and sulfur componentare contained therein, and they may contain, if desired, crystallinezeolite or other inorganic metal oxides, composite oxides, oractivators.

Since the crystalline zeolite has no ability for reducing carbonmonoxide, the terminology "carbon monoxide reduction catalyst" used inthe present specification means a composition of catalyst componentsother than crystalline zeolite.

These catalyst components may be incorporated in any order. With respectto the carbon monoxide reduction catalyst, for example, alkali metal,sulfur component, a carrier substance and an activator may be mixed withmanganese oxide and then ruthenium is supported on the resultingmixture, or alkali metal, sulfur component, a carrier and an activatormay be supported on manganese oxide likewise ruthenium. Alternatively,the above-described carrier substance may be a physical mixture, with amixture of manganese oxide, alkali metal, sulfur, and ruthenium, or thecarrier substance may support the other catalyst components. Preferablecatalysts are those wherein manganese oxide or a mixture of manganeseoxide and a carrier substance supports the other catalyst components andthose wherein the carrier substance supports the other catalystcomponents. As processes for preparation, it is possible to utilizevarious known technique, such as impregnation on manganese oxide, or gelmixing or dry mixing in case of synthesizing manganese oxide, etc.

The crystalline zeolite may be incorporated in the carbon monoxidereduction catalyst in any stage of preparation of the catalyst, and itmay be used as a mixture prepared by mixing with the prepared carbonmonoxide reduction catalyst. In the case of incorporating thecrystalline zeolite in preparation of the carbon monoxide reductioncatalyst, the catalyst may be prepared by mixing the crystalline zeolitewith manganese oxide or the carrier substance and, thereafter,supporting ruthenium and the other catalyst components on it or may beprepared by supporting crystalline zeolite on manganese oxide or acarrier substance, together with ruthenium and the other catalystcomponents. In the case of incorporating crystalline zeolite in thecarbon monoxide catalyst which has been prepared, the catalyst may beprepared, for example, by mixing the crystalline zeolite with the carbonmonoxide reduction catalyst, or by additionally adding a carriersubstance to the mixture. Preferred catalysts are those prepared byincorporating crystalline zeolite in the carbon monoxide reductioncatalyst which has been prepared.

In the following, each of the catalyst components is illustrated.Firstly, the carbon monoxide reduction catalyst is illustrated.

Manganese oxide used for preparation of the catalyst can be varioustypes of manganese oxide. Manganese oxide as used here includes oxidessuch as MnO₂, Mn₂ O₃, Mn₃ O₄, MnO, etc. These oxides may have variouscrystal structures. For example, as MnO₂, those having crystal structureof the α, β, γ, δ or ε-type are used, and an Mn₂ O₃, those havingcrystal structure of α or γ-type are used. The amount of manganese oxidein the carbon monoxide reduction catalyst is preferred to be in a rangeof from about 10 to 99.8 wt %, and preferably particularly from about 60to 99.8 wt %.

In order to improve the dispersed state of the ruthenium and to keepreactivity high, it is advantageous that the surface area of themanganese oxide is large. Further, from the viewpoint of utilizing theredox reaction of manganese oxide, in order to improve catalyticactivity and to selectively obtain the desired hydrocarbon component, itis preferred to use those manganese oxides wherein the average chargenumber of manganese is in a highly oxidized state, namely, thosecontaining a larger amount of charge component of Mn⁴⁺ or Mn³⁺ (MnO₂,Mn₂ O₃, etc.).

As methods of supporting alkali metal (e.g., lithium, sodium, potassium,cesium or rubidium) and the sulfur component on the manganese oxide, itis possible to use conventional impregnation techniques of supportingwhich comprise bringing manganese oxide into contact with a solutioncontaining an alkali metal compound or a sulfur compound, for example,by immersing manganese oxide in a solution of an alkali metal compoundor a sulfur compound to adsorb on manganese oxide, by allowing to adhereon manganese oxide by ion-exchange, by evaporating the solutioncontaining manganese oxide till dryness, or by dropwise adding thesolution onto manganese oxide. Supporting of the alkali metal and thesulfur component can be carried out before or after the supporting ofthe ruthenium or simultaneously with the supporting of the ruthenium,but it is preferred that the alkali metal and the sulfur components aresupported prior to supporting of ruthenium.

Examples of alkali metal compounds capable of using in these casesinclude alkali metal hydroxides such as LiOH, NaOH, KOH, CsOH, RbOH,etc., alkali metal carbonates such as Li₂ CO₃, Na₂ CO₃, K₂ CO₃, Cs₂ CO₃,Rb₂ CO₃, etc., inorganic salts of alkali metal such as halides,nitrates, etc., organic salts of alkali metal such as acetates, etc.,alcoholates and other various alkali metal compounds. Examples of sulfurcompounds include thiocyanates, sulfates, hydrogen sulfates,pyrosulfates, sulfites, hydrogen sulfites, thiosulfates, sulfides,polysulfides, etc., of various metals or ammonium cation, sulfurcontaining hydrocarbons, sulfuric acid esters, etc.

The sulfur component may be added to a catalyst conposition in whichcatalyst components other than the sulfur component have beenincorporated. For example, it is possible to add the sulfur component tothe catalyst by supplying sulfur in the state of being a sulfurcompound, such as gaseous sulfur compounds, e.g., hydrogen sulfide,carbon disulfide, carbonyl sulfide, etc., or sulfur-containinghydrocarbons, etc., through the prepared catalyst, preferably, theprepared catalyst charged in a reactor.

Addition of the alkali metal component and the sulfur component may becarried out at any time during preparation or after preparation ofmanganese oxide, and before, after, or during supporting Ru as activemetal. In case of using H₂ S, CS₂, etc., addition of the sulfur can becarried out after reduction of the catalyst (after combination withcrystalline zeolite) or during the carbon monoxide reduction reaction.

Addition of the alkali metal and the sulfur may be carried out in anyorder. Further, the alkali metal and the sulfur can be added at the sametime by dissolving a compound containing both the alkali metal and thesulfur component, e.g., alkali metal sulfide, sulfur-containing acidsalts of alkali metal (examples in the case of using potassium compoundsinclude K₂ SO₄, K₂ S₂ O₇, K₂ S, K₂ S₅, K₂ SO₃, KHSO₃, K₂ S₂ O₃, KSCN,KHSO₄, etc.), etc., in a suitable solvent.

Alternatively, desired amounts of alkali metal and the sulfur componentmay be incorporated in the case of synthesizing manganese oxide. Forexample, it may be carried out by a process which comprisesincorporating alkali metal in case of synthesizing α-type MnO₂ byelectrolytic oxidation, or by a process which comprises washing withwater so as to remain a suitable amount of alkali metal or sulfateradical in case of synthesizing γ-type MnO₂ by air oxidation ofmanganese carbonate.

Preferred carbon monoxide reduction catalysts of the present inventionare those wherein ruthenium is supported on manganese oxide containingsmall amounts of alkali metal and sulfur.

The preferred amount of alkali metal to be incorporated is generally ina range of from about 0.01 to 8 wt %, and preferably from 0.05 to 6 wt %(calculated as metal), based on the total weight of the carbon monoxidereduction catalyst. The preferred amount of sulfur to be incorporated isin a range of from about 0.001 to 3 wt %, and preferably from 0.07 to1.5 wt % (calculated as S), based on the total weight of the carbonmonoxide reduction catalyst. If the amount of either the alkali metal orthe sulfur component is too small in the catalyst, the desiredhydrocarbon component cannot be selectively obtained, and temperaturedependence of distribution of the product becomes high. If the amount ofone component thereof is too large, significant improvement of catalyticactivity is not obtained.

Other sparingly soluble substances which do not substantially damage thehydrocarbon synthesizing characteristic of ruthenium-containingcatalysts can be incorporated in the catalyst as carrier substances. Forexample, it is possible to mix inorganic metal oxides such as TiO₂,SiO₂, Al₂ O₃, Cr₂ O₃, V₂ O₅, WO₃, MoO₃, etc., or natural clay mineralswith manganese oxide. It is also possible to mix such metal oxides orclay minerals with manganese oxide containing alkali metal and sulfur,to mix them with manganese oxide containing alkali and sulfur whichsupports ruthenium, or to support them on another carrier. Further, itis possible to support desired amounts of manganese oxide, alkali metal,sulfur, and ruthenium on these carrier substances. A preferred amount ofthe above described carrier substances to be incorporated is in a rangeof from about 0.01 to 90 wt %, and particularly preferably from about 5to 60 wt %, based on the whole weight of the carbon monoxide reductioncatalyst. These carrier substances are effective for increasing thesurface area of the catalyst, increasing mechanical strength, improvingmolding property, improving removal of reaction heat or reducing theprice of the catalyst.

Supporting of ruthenium on the mixture of manganese oxide, alkali metal,and sulfur can be carried out by utilizing conventional impregnationtechniques for supporting a substance, which comprises bringing theabove described mixture into contact with a solution containing aruthenium compound, for example, by immersing the above describedmixture in a solution of a ruthenium compound to adsorb on the mixture,by allowing to adhere on the mixture by ion-exchange, by depositing onthe mixture by adding precipitants such as alkalis, by evaporating thesolution containing the mixture till dryness, or by dropwise adding thesolution onto the mixture. Examples of ruthenium compounds capable ofuse in such cases include those soluble in water, such as rutheniumchloride, ruthenium nitrate, ruthenium acetate, ruthenium hexaammoniumchloride ((Ru(NH₃)₆)Cl₁₃), etc., and those soluble in organic solvents,such as ruthenium carbonyl clusters, ruthenium acetylacetonate (Ru(C₅ H₇O₂)₃), etc.

The amount of ruthenium to be incorporated is generally in a range offrom about 0.1 to 50 wt %, preferably from about 0.1 to 30 wt %, andmost preferably from 0.5 to 25 wt % (calculated as Ru), based on thetotal weight of the carbon monoxide reduction catalyst. If the amount ofruthenium to be incorporated is too small, catalytic activity becomeslow, and if it is too large, selectivity for producing the desiredhydrocarbon component deteriorates. Ruthenium in the catalyst isgenerally in a state such that the greater part is simple substance ofmetal (i.e., metallic state), but it may be in a state of a compoundsuch as oxide.

Addition of ruthenium is not restricted to the above case of adding tothe mixture of manganese oxide, alkali metal, and sulfur, and it ispossible to incorporate ruthenium in a produced mixture after the abovedescribed mixture is combined with crystalline zeolite.

Further activators may be incorporated in the catalyst in order toincrease activity. Examples of the activators include magnesium, zinc,copper, iron, etc., which may be incorporated in the catalyst in a stateof simple substance of metal or a state of compound such as chloride,ammonium salt, nitrate, oxide, etc. Examples of activator component usedas raw materials when preparing the catalyst include magnesium chloride,zinc chloride, copper chloride, iron chloride, iron nitrate, etc. Theamount of the activator to be incorporated is preferred to be in a rangeof from about 0.01 to 35 wt %, and particularly preferably from about0.1 to 20 wt % (calculated as metal), based on the total weight of thecarbon monoxide reduction catalyst. A preferred sum total amount of theactivator and the carrier substance is in a range of from about 0.01 to90 wt % (base on the total weight of the carbon monoxide reductioncatalyst). The activator may be added in case of synthesizing manganeseoxide or may be mixed with manganese oxide, but it is preferred to addbefore or after supporting ruthenium after synthesizing manganese oxide,or simultaneously with supporting ruthenium. The activator can be addednot only at preparation of the carbon monoxide reduction catalyst butalso to the composite of the carbon monoxide reduction catalyst afterpreparation thereof.

In the following, the above described crystalline zeolite isillustrated.

Zeolite used as the crystalline zeolite in the present inventionincludes crystalline aluminosilicates, crystalline silicates synthesizedby replacing a part or the whole of aluminium atoms in crystallinealuminosilicate with other metals, for example, trivalent metals such asiron, chromium, vanadium, bismuth, lanthanum, cerium, titanium, boron,gallium, etc. and crystalline silicates composed of 90 wt % or more ofsilica which hardly contain aluminium atoms. These crystalline zeolitesmay be any of H type zeolites, wherein the cation capable of carryingout ion-exchange is hydrogen, zeolites wherein a part or all of thehydrogen is exchanged for alkali metal such as Li, Na, K, Rb, Cs, etc.,or alkaline earth metal such as Ca, Ba, Mg, Sr, etc., and zeolitecontaining these metals.

Examples of these crystalline zeolites include erionite, offretite, andferrierite, which have a pore diameter of about 5 Å, faujasite typezeolite X or Y and mordenite type zeolite, which have a pore diameter ofabout 9 Å, and ZSM series zeolite which has an intermediate pore in arange of from about 5 to 9 Å of pore diameter, and has a ratio of silicato alumina of about 10/1 or more. These crystalline zeolites have beendescribed in detail in Saikin no zeolite gijutsu to oyo no shinposogoshirryoshu, pages 46-57, published by Nippon Gijutsukeizai CenterShuppanbu, Jan. 11, 1982; Zeolite, pages 29-32 and 46-47, edited byHiroshi Takahashi et al, published by Kodansha Co., Feb. 1, 1975; andJapanese Patent Application (OPI) No. 70828/82.

Of these zeolites, the most suitable zeolites for obtaining the gasolinefraction in a high yield are zeolites having a pore diameter of from 5to 9 Å. Zeolites of this kind include ZSM series zeolites having a molarratio of silica to alumina of 10/1 or more, such as ZSM-5, ZSM-11,ZSM-12, ZSM-21, ZSM-35, ZSM-38, etc., which were developed by Mobil OilCorp., zeolites composed of silica-iron-alumina showing a X-raydiffraction pattern analogous to ZSM-5 which were developed by ShellInternational Research Co., ZSM-5 type crystalline zeolites which areproduced by a different process from that of ZSM-5 but have the sameX-ray diffraction pattern as that of ZSM-5, zeolites wherein a part orthe whole of aluminum in the above described zeolites are replaced withother trivalent metals, and those wherein a part or the whole of H-typezeolites are replaced with alkali metal or alkaline earth metal byion-exchanging.

The crystalline zeolites generally contain sodium, potassium or organicnitrogen cations as cations capable of carrying out ion-exchange.However, in case of using them for the conversion reaction of thepresent invention, it is preferred that at least 50% of these cationsare replaced with hydrogen ions, alkaline earth ions, rare earth ions,transition metal ions, etc., so that acid sites appear. Generally, thecation exchange processing can be carried out by the known ion-exchangeart which comprises processing with an aqueous solution containingcations for exchanging.

Further, crystalline zeolites containing organic nitrogen cations orammonium ions can be easily converted into hydrogen ion type by heatingat a range of 400° to 700° C. in the air to decompose and calcine theorganic nitrogen cations or ammonium ions.

Combination of the above described carbon monoxide reduction catalystand the crystalline zeolite can be carried out by processes knownhitherto. Examples include a process which comprises physically mixingthe carbon monoxide reduction catalyst with the crystalline zeolite toform a homogeneous mixture, a process wherein the former part of thereactor is filled with the carbon monoxide reduction catalyst and thelatter part thereof is filled with the crystalline zeolite, and aprocess wherein the reactor is filled with the carbon monoxide reductioncatalyst and the crystalline zeolite one after another so as to bepresent in multilayers. Further, a two-stage process wherein the carbonmonoxide reduction catalyst and the crystalline zeolite are charged indifferent reactors, respectively, can be used, too. The carbon monoxidereduction catalyst, the crystalline zeolite, and the catalystcomposition composed of both of them may have any desired shape, forexample, powder, granules, extrusion moldings, etc. In order to improvemolding property or for removal of reaction heat, the above describedcarrier substances may be added. The rate of the carbon monoxidereduction catalyst in the catalyst composition is from about 5 to 95 wt%, and preferably from about 30 to 80 wt %, based on the total amount ofcarbon monoxide reduction catalyst and crystalline zeolite. If the rateof the carbon monoxide reduction catalyst is too small, yield of thedesired hydrocarbons is reduced. If the rate of the crystalline zeoliteis too small, it becomes difficult to obtain the desired liquidhydrocarbons such as gasoline having a high octane value and excellentquality, kerosene, or gas oil in a good yield.

The carbon monoxide reduction catalyst containing manganese oxide,alkali metal, sulfur and ruthenium as essential components, thecrystalline zeolite, or the catalyst composition obtained by combiningboth of them, produced as described above, is dried after molding by aconventional manner or without molding. The drying can be carried out byholding at room temperature to 300° C. for about 10 to 48 hours. Themost suitable drying process is that which comprises heating in air atabout 90° to 110° C. for few hours after drying at room temperature, orimmediately heating in air at about 90° to 110° C. for few hours. Thedried catalyst composition may be calcined by a conventional manner, asoccasion demands.

In the process of the present invention, the carbon monoxide reductioncatalyst free from crystalline zeolite and comprising ruthenium, alkalimetal, sulfur, and manganese oxide, which is used in case of obtaininghydrocarbons rich in olefins as the desired product causes variation ofdistribution of the product, if it is calcined or not in the air at acertain elevated temperature prior to reduction by a hydrogen gas andintroduction of a synthesis gas. In the case of obtaining hydrocarbonsrich in C₂ to C₄ lower olefins, it is preferred that the calciningprocessing in the air is omitted, and it is introduced directly into areduction step using a H₂ gas. In the case of obtaining hydrocarbonsrich in high boiling point olefins, for example, olefins having from 5to 40 carbon atoms, it is calcined at a temperature of about 600° C. orless, and preferably at from about 300° to 600° C. The calcining time ispreferred to be in a range of from about 30 minutes to 24 hours. Thecalcining may be carried out by any manner of calcining only thesubstrate for supporting ruthenium prior to supporting ruthenium,calcining the catalyst after supporting ruthenium, or calcining thesubstrate for supporting ruthenium together with the catalyst. However,the most preferred manner is to calcine after supporting ruthenium. Ifcalcining is carried out at a high temperature condition of above 600 °C., the catalytic activity deteriorates and the selectivity forformation of olefins deteriorates.

In the process of the present invention, the composite catalyst composedof the carbon monoxide reduction catalyst comprising ruthenium, alkalimetal, sulfur, and manganese oxide, and crystalline zeolite, which isused in case of obtaining hydrocarbons rich in liquid hydrocarbons asthe desired product, does not cause great variation of distribution ofthe product if it is calcined or not prior to use for the reaction.

The calcining is preferably carried out at a temperature of from 150° to600° C., and more preferably at from about 300° to 600° C., for fromabout 30 minutes to 48 hours. Drying or calcining may be carried out inany stage of preparation of the carbon monoxide reduction catalyst.

The catalyst composition prepared as described above is preferablysubjected to reduction treatment in a reducing atmosphere such ashydrogen or carbon monoxide at a temperature of about 300° C. or more,preferably about 400° C. or more, for about 0.5 to 4 hours, prior toapplying a synthesis gas. In this case, it is preferred to keep thesystem under an atmospheric pressure of about 1 atm. In the case ofcarrying out reduction processing with hydrogen, etc., the catalyst maybe subjected to surface processing by a pre-treatment step wherein anoxygen-containing compound such as water, methanol, ethanol, etc., orhydrogen sulfide is introduced together with hydrogen, etc., to carryout activation and sulfurization, by which it becomes possible tocontrol distribution of the product.

With respect to reaction operating conditions for the process of thepresent invention, the pressure is generally in a range of 0 to 100kg/cm² G (gauge pressure), preferably from 0 to 30 kg/cm² G, and mostpreferably from 0 to 20 kg/cm² G. The reaction may be carried out underreduced pressure. The temperature is in a range of from about 100° to500° C., preferably from about 200° to 450° C., and most preferably fromabout 250° to 400° C. The molar ratio of hydrogen to carbon monoxide (H₂/CO) is in a range of from about 0.1/1 to 10/1, and preferably fromabout 0.5/1 to 4/1, and most preferably 0.5/1 to 1/1, which means thatthe gas mixture contains carbon monoxide in a slightly excess amount.The space velocity (GHSV) of the feed gas is in a range of from about100 hr⁻¹ to 20000 hr⁻¹. The whole or a part of the gas mixture exhaustedfrom the reactor is recycled to the apparatus after the formedhydrocarbon product is removed.

The catalyst used in the process of the present invention is generallyapplied as a fixed bed. However, it can be applied to a fluidized bedand a suspension bed wherein it is used in a finely divided state.Further, the catalyst may be removed from the reactor in order toregenerate continuously or discontinuously. Regeneration of the catalystis carried out by burning it with the air in a special container toremove impurities attaching to the surface of the catalyst, andsubsequently reducing it by a known method stated above.

It is believed that, in the reduction step of the pre-treatment of thecatalyst or during the reaction, the greater part of the rutheniumcompound in the catalyst becomes a simple substance of metal, and a partthereof becomes sulfide or oxide. Further, it is believed that, theinitial form of manganese oxide in preparation of the catalyst, isconverted into another crystal form or another manganese oxide duringthe reaction. In the catalyst of the present invention, ruthenium andmanganese oxide are believed to act as a composite catalyst, and alkalimetal and sulfur are believed to act as a promotor.

In the process of the present invention, hydrocarbons rich inunsaturated hydrocarbons are selectively formed from carbon monoxide andhydrogen when the catalyst used is a carbon monoxide reduction catalystcomposed of sparingly soluble manganese oxide wherein alkali metal andsulfur are coexistent and ruthenium. Particularly, hydrocarbons rich ingaseous lower olefins are selectively obtained in a good yield under areaction pressure of 0 to 5 kg/cm² G using a catalyst which is notsubjected to calcining processing, and hydrocarons rich in higherunsaturated hydrocarbons are selectively obtained in a good yield undera reaction pressure of about 5 Kg/cm² G or more using a catalyst whichis subjected to calcining processing. In the process of the presentinvention, though distribution of the formed hydrocarbon compoundsfollows the Schultz-Flory law with respect to C₃ or more fractions, theamount of methane formed, which is inevitable in the carbon monoxidereduction reaction using a conventional ruthenium type catalyst, isextremely small, and hydrocarbons rich in C₂ or more unsaturatedhydrocarbons are obtained in a good yield. Further, since the catalystof the present invention has good sulfur resistance, feed gasescontaining sulfur components as impurities can be used.

When the catalyst composed of the above described carbon monoxidereduction catalyst and crystalline zeolite is used in the process of thepresent invention, olefins formed by the carbon monoxide reductioncatalyst are secondarily converted, and consequently liquidhydrocarbons, and particularly hydrocarbons comprising a gasolinefraction as a main component, can be obtained from the synthesis gas ina high selectivity and a high yield. Since the resulted gasolinefraction has a high aromatic hydrocarbon content, it can be used as fuelfor cars having a high octane value or as petrochemical raw material.Further, since this catalyst also has good sulfur resistance, feedgasses containing sulfur components as impurities can be used.

In the following, the present invention is illustrated with reference toexamples. In the following examples, the molar ratio of H₂ / CO in thereaction conditions was 1.0/1 unless otherwise stated.

MnO₂, MnO, Mn₂ O₃ and Mn₃ O₄ used were those available on the marketunless otherwise stated. A portion of δ-type and a portion of β-typeMnO₂ was produced according to the following reference example. In thecase of using such MnO₂ obtained according to reference example, it isnoted in the example.

REFERENCE EXAMPLE 1

γ-type manganese dioxide was synthesized as follows. A hot aqueoussolution mixture (60° C.) of 1N-manganese sulfate (II) and 0.2N-sulfuricacid was electrolyzed under a condition of current density 3.0 A/dm²using an anode of platinum to form electrolytic manganese dioxide on theelectrode. It was separated from the electrode and sufficiently washedwith water to remove the attached electrolyte. Thereafter, it wasneutralyzed using a 10% solution of NaHCO₃. Then it was stirred in a 5%solution of NH₄ Cl as a peptization inhibitor at a temperature of 60° C.for 1 hour, and suction filtration was repeatedly carried out severaltimes to reduce the S content in the sample to 0.06 wt % or less. Then,it was dried in a constant-temperature bath at 80° to 100° C. to obtainγ-type manganese dioxide.

REFERENCE EXAMPLE 2

β-type manganese dioxide was synthesized by heating manganese sulfate(II) hexahydrate in air at 150° to 190° C. for 2 to 3 days, andthereafter washing with boiling diluted nitric acid and then withboiling water, and further heating at a temperature of 450° to 500° C.

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1

Ru-Na-S/MnO₂ catalyst (1) was prepared as follows. As manganese oxide,commercially available amorphous MnO₂ (guaranteed reagent, surface area150.9 m² /g) which did not show a diffraction pattern in X-raydiffractiometry was used.

30 g of the amorphous MnO₂ powder was stirred in 80 ml of an aqueoussolution of sulfuric acid having a pH of 4.8 at room temperature (about25° C.) for about 24 hours. After it was filtered and dried, it wasimmersed in water (80 ml). A concentrated aqueous solution of NaOH wasadded dropwise to control the pH at 9.3. After stirring for about 24hours, it was dried in an oven at 90° to 100° C. 22.1 g of the Na-S/MnO₂mixture prepared as described above was immersed in a solution preparedby dissolving 2.28 g of ruthenium chloride in 10 ml of a mixture ofequal volumes of water and ethanol. After standing for about 24 hours,the solvent was removed under a nitrogen stream and the residue wasdried in an oven at 90° to 100° C. to prepare a catalyst (1).

The catalyst (1) prepared as described above contained 0.45 wt % of Na,0.26 wt % of S and 4.0 wt % of Ru. 2 ml (2.60 g) of this catalyst wasplaced in a reactor, and it was subjected to reduction processing at400° C. for 2 hours under a hydrogen gas atmosphere. Subsequently, itwas cooled to a temperature of lower than the reaction temperature(about 100° C.) in a hydrogen gas. Thereafter, a reaction gas consistingof carbon monoxide and hydrogen (molar ratio of H₂ /CO=1) was fed to thecatalyst layer as a cocurrent down-stream, and catalytic performance wasevaluated.

Reaction conditions and composition of the product are shown in Table 1.

For comparison, a Ru-Na/MnO₂ catalyst (3) which was not subjected toprocessing with the aqueous solution of H₂ SO₄, a Ru-S/MnO₂ catalyst (2)which was not subjected to processing with an aqueous solution of NaOH,and a Ru/MnO₂ catalyst (4) which was not subjected to processing witheither of the aqueous solutions of H₂ SO₄ or NaOH were prepared in thesame manner as for the above described catalyst (1), and they wereanalogously evaluated. The results are shown in Table 1.

It should be noted that, in the case of the Ru-Na-S/MnO₂ catalyst, theamount of methane formed is very low, the ratio of olefin/paraffin inthe C₂ fraction is remakably improved, and the selectivity for C₂ to C₄lower olefins is particularly high, as compared with the cases of thecatalysts which do not contain alkali metal, sulfur, or both of them.

                                      TABLE 1                                     __________________________________________________________________________                 Reaction conditions                                                           Temp-       CO  Selectivity              Ratio                                                                             Amount                           per-                                                                             Pressure con-   Hydro-                                                                            Distribution of hydrocarbons                                                                    ofrmed                                                                            of C.sub.2 to       Catalyst     ature                                                                            (kg/ GHSV                                                                              version                                                                           CO.sub.2                                                                         carbon                                                                            (wt %)            C.sub.2.sup.=                                                                     C.sub.4             Composition  (°C.)                                                                     cm.sup.2 G)                                                                        (hr.sup.-1)                                                                       (%) (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                          C.sub.4                                                                          C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                      formed             __________________________________________________________________________    Example 1:                                                                    (1)                                                                             4% Ru--0.45% Na--                                                                        400                                                                              0    1200                                                                              29.1                                                                              24.1                                                                             75.9                                                                              17.9                                                                             45.0                                                                             26.6                                                                             7.4                                                                              2.7                                                                             0.3                                                                             0.1                                                                             32.40                                                                             79.0                  0.26% S/MnO.sub.2                                                           (1)                                                                             4% Ru--0.45% Na--                                                                        400                                                                              9.3  3000                                                                              38.8                                                                              35.5                                                                             64.5                                                                              25.4                                                                             29.8                                                                             25.6                                                                             11.0                                                                             4.8                                                                             2.3                                                                             1.1                                                                             2.03                                                                              66.4                  0.26% S/MnO.sub.2                                                           Comparative Example 1:                                                        (2)                                                                             4% Ru--0.26% S/                                                                          400                                                                              0    1200                                                                              24.8                                                                              23.8                                                                             76.2                                                                              59.5                                                                             27.8                                                                             10.4                                                                             1.8                                                                              0.4                                                                             0.1                                                                             0 0.61                                                                              39.9                  MnO.sub.2                                                                   (3)                                                                             4% Ru--0.51% Na/                                                                         400                                                                              0    1200                                                                              43.2                                                                              29.8                                                                             70.2                                                                              46.8                                                                             31.8                                                                             17.2                                                                             3.3                                                                              0.8                                                                             0.1                                                                             0 0.55                                                                              52.3                  MnO.sub.2                                                                   (4)                                                                             4% Ru/MnO.sub.2                                                                          400                                                                              0    1200                                                                              45.2                                                                              33.6                                                                             66.4                                                                              57.5                                                                             31.9                                                                              8.6                                                                             1.2                                                                              0.6                                                                             0.2                                                                             0 0.1 41.7                (4)                                                                             4% Ru/MnO.sub.2                                                                          400                                                                              11.5 3000                                                                              50.2                                                                              24.1                                                                             75.9                                                                              42.5                                                                             25.9                                                                             18.9                                                                             7.5                                                                              3.1                                                                             1.5                                                                             0.6                                                                             0.1 52.3                __________________________________________________________________________     Notes:                                                                        (1) The ratio of C.sub.2.sup.= /C.sub.2.sup.- shows the ratio of              ethylene/ethane (wt/wt) formed. Hereinafter, it has the same meaning.         (2) The amount of C.sub.2 to C.sub.4 formed shows the total of C.sub.2,       C.sub.3, and C.sub.4 in the distribution of the product. Hereinafter, it      has the same meaning.                                                         (3) 4% Ru--0.45% Na--0.26% S/MnO.sub.2 in Catalyst (1) means the catalyst     which consists of 4.0 wt % of Ru, 0.45 wt % of Na, 0.26 wt % of S and the     balance of MnO.sub.2. The same applies to the subsequent examples and         tables.                                                                       (4) Oxygencontaining compounds are formed. However, since the amount of       them is very small, selectivity for them is neglected. The same applied t     the subsequent examples and tables.                                      

EXAMPLE 2 AND COMPARATIVE EXAMPLE 2

Ru-containing catalysts (5), (6), (7) and (8) prepared using variousmanganese oxides containing the sulfur component and alkali metal whichwere supported by adjusting pH in the same manner as that for thecatalyst (1) of Example 1 (manganese oxides used: γ-MnO₂ in ReferenceExample 1 (surface area 223.1 m² /g), commercially available β-MnO₂(guaranteed reagent, high degree of crystallinity, surface area 10.5 m²/g), Mn₂ O₃ (guaranteed reagent, surface area 50.3 m² /g) and Mn₃ O₄(guaranteed reagent, surface area 18.3 m² /g)), were used for carryingout the reaction. The results are shown in Table 2.

In the example of the present invention, it is understood that theamount of methane formed is small, and particularly, the ratio ofolefin/paraffin in the C₂ fraction and the amount of C₂ to C₄ formed areimproved in manganese oxide type catalysts (5), (6), (7) and (8), ascompared with catalysts (9), (10), (11) and (12), respectively, incomparative example which do not contain alkali metal and the Scomponent, and that Ru/manganese oxide type catalysts containing thealkali metal and S show an excellent effect of forming lower olefins.

                                      TABLE 2                                     __________________________________________________________________________                  Reaction conditions                                                           Tem-        CO  Selectivity             Ratio                                                                             Amount                            per-                                                                             Pressure con-   Hydro-                                                                            Distribution of hydro                                                                          ofrbons                                                                           of                  Catalyst      ature                                                                            (kg/ GHSV                                                                              version                                                                           CO.sub.2                                                                         carbon                                                                            formed (wt %)    C.sub.2.sup.=                                                                     C.sub.2 to                                                                    C.sub.4             Composition   (°C.)                                                                     cm.sup.2 G)                                                                        (hr .sup.-1)                                                                      (%) (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                          C.sub.4                                                                         C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                     formed              __________________________________________________________________________    Example 2:                                                                    (5)                                                                              4% Ru--0.51% Na--                                                                        400                                                                              0    1500                                                                              20.2                                                                              24.3                                                                             75.7                                                                              17.9                                                                             45.0                                                                             26.6                                                                             7.4                                                                             2.7                                                                             0.3                                                                             0.1                                                                             54.5                                                                              79.0                   0.21% S/MnO.sub.2                                                             (γ-type)                                                             (5)                                                                              4% Ru--0.51% Na--                                                                        400                                                                              10.8 2400                                                                              41.8                                                                              16.4                                                                             83.6                                                                              30.6                                                                             32.6                                                                             22.6                                                                             8.9                                                                             3.4                                                                             1.3                                                                             0.6                                                                             4.35                                                                              64.1                   0.21% S/MnO.sub.2                                                             (γ-type)                                                             (6)                                                                              1% Ru--0.85% K--                                                                         400                                                                              0     150                                                                              14.3                                                                              27.8                                                                             72.2                                                                              72.1                                                                             21.2                                                                              5.9                                                                             0.7                                                                             0.1                                                                             0 0 1.56                                                                              27.8                   0.32% S/MnO.sub.2                                                             (β-type)                                                              (7)                                                                              4% Ru--1.45% Rb--                                                                        400                                                                              0    1500                                                                              22.2                                                                              18.6                                                                             81.4                                                                              23.4                                                                             44.7                                                                             23.9                                                                             5.6                                                                             1.9                                                                             0.4                                                                             0.1                                                                             16.55                                                                             74.2                   0.25% S/Mn.sub.2 O.sub.3                                                   (8)                                                                              1% Ru--0.33% Na--                                                                        400                                                                              0     150                                                                               7.6                                                                               7.7                                                                             92.3                                                                              61.6                                                                             27.4                                                                              9.0                                                                             1.4                                                                             0.5                                                                             0.1                                                                             0 2.49                                                                              37.8                   0.19% S/Mn.sub.3 O.sub.4                                                   Comparative Example 2:                                                        (9)                                                                              4% Ru/MnO.sub.2                                                                          400                                                                              0    1500                                                                              22.7                                                                              30.2                                                                             69.8                                                                              27.3                                                                             38.5                                                                             23.2                                                                             8.2                                                                             2.3                                                                             0.4                                                                             0.1                                                                             25.70                                                                             69.9                   (γ-type)                                                             (9)                                                                              4% Ru/MnO.sub.2                                                                          400                                                                              12.1 2400                                                                              44.6                                                                              19.7                                                                             80.3                                                                              34.4                                                                             28.3                                                                             21.0                                                                             9.4                                                                             4.1                                                                             1.9                                                                             0.9                                                                             0.98                                                                              58.7                   (γ-type)                                                             (10)                                                                             1% Ru/MnO.sub.2                                                                          400                                                                              0     150                                                                              15.7                                                                              20.2                                                                             79.8                                                                              82.6                                                                             13.8                                                                              2.1                                                                             1.4                                                                             0.1                                                                             0 0 0.21                                                                              17.3                   (β-type)                                                              (11)                                                                             4% Ru/Mn.sub.2 O.sub.3                                                                   400                                                                              0    1500                                                                              25.5                                                                              20.7                                                                             79.3                                                                              48.7                                                                             32.4                                                                             15.3                                                                             3.0                                                                             0.6                                                                             0 0 2.09                                                                              50.7                (12)                                                                             1% Ru/Mn.sub.3 O.sub.4                                                                   400                                                                              0     150                                                                               9.7                                                                               9.8                                                                             90.2                                                                              80.8                                                                             13.9                                                                              4.5                                                                             0.7                                                                             0.1                                                                             0 0 1.00                                                                              19.1                __________________________________________________________________________

EXAMPLE 3 AND COMPARATIVE EXAMPLE 3

20.0 g of a manganese oxide powder obtained by calcining a comerciallyavailable MnO powder (guaranteed reagent, surface area 11.8 m² /g) inair at 550° C. for 8 hours was processed with aqueous solutions of H₂SO₄ and NaOH in the same manner as for the catalyst (1) in Example 1.After supporting Na and S components, ruthenium was applied to prepare acatalyst (13), and the reaction was carried out using it. The resultsare shown in Table 3. When calcining was carried out as described above,MnO changed color from initial yellowish green to grayish brown. Thischange meant that a part of the MnO was converted into Mn₂ O₃ and/orMnO₂.

It should be noticed that, in the example of the present invention, theselectivity for C₂ to C₄ lower olefins is remarkably improved ascompared with the case of using the catalysts (14) and (15) which do notcontain both alkali metal and S. The catalyst (14) is different from thecatalyst (15) in that the catalyst (14) was prepared using MnO clacinedin air at 550° C. for 8 hours, and the catalyst (15) was prepared usingMnO which was not calcined. The catalysts (13) and (14) prepared usingMnO calcined in air form a remarkably small amount of methane ascompared with the Ru/MnO catalyst (15).

                                      TABLE 3                                     __________________________________________________________________________                  Reaction conditions                                                           Tem-        CO  Selectivity             Ratio                                                                             Amount                            per-                                                                             Pressure con-   Hydro-                                                                            Distribution of hydrocarbons                                                                   of  of                  Catalyst      ature                                                                            (kg/ GHSV                                                                              version                                                                           CO.sub.2                                                                         carbon                                                                            formed (wt %)    C.sub.2.sup.=                                                                     C.sub.2 to                                                                    C.sub.4             Composition   (°C.)                                                                     cm.sup.2 G)                                                                        (hr.sup.-)                                                                        (%) (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                          C.sub.4                                                                         C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                      formed             __________________________________________________________________________    Example 3:                                                                    (13)                                                                             2% Ru--0.41% Na--                                                                        400                                                                              0    300 28.8                                                                              22.1                                                                             77.9                                                                              25.5                                                                             41.8                                                                             25.7                                                                             5.1                                                                             1.2                                                                             0.7                                                                             0 16.23                                                                             72.6                   0.26% S/550 MnO                                                            (13)                                                                             2% Ru--0.41% Na                                                                          400                                                                              0    600 18.0                                                                              17.3                                                                             82.7                                                                              24.3                                                                             46.7                                                                             22.5                                                                             4.7                                                                             1.2                                                                             0.6                                                                             0 27.05                                                                             73.9                   0.26% S/550 MnO                                                            Comparative Example 3:                                                         (14)                                                                            2% Ru/550 MnO                                                                            400                                                                              0    300 30.8                                                                               5.4                                                                             94.6                                                                              30.3                                                                             45.0                                                                             20.1                                                                             3.7                                                                             0.8                                                                             0.1                                                                             0  0.42                                                                             68.8                (15)                                                                             2% Ru/MnO  400                                                                              0    300 18.4                                                                               1.9                                                                             98.1                                                                              43.4                                                                             37.7                                                                             15.4                                                                             2.9                                                                             0.6                                                                             0 0  0.97                                                                             56.0                __________________________________________________________________________

EXAMPLE 4 AND COMPARATIVE EXAMPLE 4

A Ru-K-S/β-MnO₂ type catalyst was prepared as follows. As manganeseoxide, β-MnO₂ synthesized by the method of Reference Example 2 was used(which had slightly inferior crystallinity; surface area 34.9 m² /g).100 g of this β-MnO₂ powder was immersed in 100 ml of an aqueoussolution containing 0.61 g of KSCN. After standing at room temperaturefor about 24 hours, the solvent was removed by a water aspirator anddrying was carried out at 80° to 100° C. in an oven. To 10 g of theK-S/β-MnO₂ mixture prepared as described above, 6 ml of a solutioncontaining 0.45 g of ruthenium chloride in a mixture of water-ethanol inequal volume was added dropwise. After standing at room temperature forabout 24 hours, the solvent was removed under a nitrogen stream, anddrying was carried out at 90° to 110° C. in an oven to obtain a catalyst(16). The catalyst (16) prepared as described above contained 0.24 wt %of K, 0.2 wt % of S and 2.0 wt % of Ru. A catalyst (17) containingpotassium and sulfur was prepared by the same manner as that for thecatalyst (16), except that K₂ SO₄ was used as the K-S containingcompound instead of KSCN. Using these catalysts, the reaction wascarried out by the same manner as in Example 1. Reaction conditions andresults are shown in Table 4. It is understood from the results shown inTable 4 that formation of methane is remarkably restricted andselectivity for C₂ to C₄ lower olefins is remarkably improved, even if acompound containing both of alkali metal and sulfur is added tomanganese oxide.

                                      TABLE 4                                     __________________________________________________________________________                 Reaction conditions                                                           Tem-        CO  Selectivity              Ratio                                                                             Amount                           per-                                                                             Pressure con-   Hydro-                                                                            Distribution of hydrocarbons                                                                    ofrmed                                                                            of                  Catalyst     ature                                                                            (kg/ GHSV                                                                              version                                                                           CO.sub.2                                                                         carbon                                                                            (wt %)            C.sub.2.sup.=                                                                     C.sub.2 to                                                                    C.sub.4             Composition  (°C.)                                                                     cm.sup.2 G)                                                                        (hr.sup.-1)                                                                       (%) (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                          C.sub.4                                                                          C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                      formed             __________________________________________________________________________    Example 4:                                                                    (16)                                                                             2% Ru--0.24% K--                                                                        400                                                                              0    1200                                                                              29.3                                                                              44.2                                                                             55.7                                                                              19.6                                                                             33.4                                                                             28.7                                                                             11.7                                                                             5.0                                                                             1.2                                                                             0.4                                                                             7.82                                                                              73.8                   0.2% S/β-MnO.sub.2                                                    (17)                                                                             2% Ru--0.5% K--                                                                         400                                                                              0    1200                                                                              30.3                                                                              41.0                                                                             59.0                                                                              16.4                                                                             33.3                                                                             28.3                                                                             11.6                                                                             5.3                                                                             4.4                                                                             0.7                                                                             5.18                                                                              73.2                   (0.2% S/β-MnO.sub.2                                                   Comparative Example 4                                                         (18)                                                                             2% Ru/β-MnO.sub.2                                                                  400                                                                              0    1200                                                                              32.5                                                                              35.6                                                                             64.4                                                                              65.4                                                                             23.7                                                                              8.2                                                                              1.7                                                                             0.8                                                                             0.1                                                                             0 1.71                                                                              33.6                __________________________________________________________________________

EXAMPLE 5

12 g of γ-type MnO₂ prepared according to the process shown in ReferenceExample 1 (which was prepared in a different batch from that of theγ-type MnO₂ used in Example 2; surface area 196 m² /g) was immersed in80 ml of an aqueous solution of sulfuric acid having pH 3.9, and it wasstirred at room temperature for 15 hours. After it was filtered, washedwith water and dried, it was immersed in 12 ml of an aqueous solutioncontaining 0.51 g of KCl. After standing for about 24 hours, the solventwas removed by a water-aspirator, and drying was carried out at 90° to110° C. in an oven. The K-S/γ-MnO₂ mixture prepared as described abovewas impregnated with ruthenium chloride by the same manner as shown inExample 1 to obtain a Ru-K-S/γ-MnO₂ catalyst (19). A catalyst (20) wasprepared by the same manner as in Catalyst (19), except that KNO₃ wasused instead of KCl so that anion of alkali metal salt was changed.Using these catalysts, the reaction was carried out by the same manneras in Example 1. The reaction conditions and results thereof are shownin Table 5. It is obvious from the results of Table 5 that neitherdistribution of the reaction product nor olefin selectivity isinfluenced by the alkali metal source, if the anion of alkali metal saltis changed, and the selectivity thereof is shown as a synergistic effectof alkali metal and sulfur as shown in Example 1.

                                      TABLE 5                                     __________________________________________________________________________                 Reaction conditions                                                           Tem-             Selectivity             Ratio                                                                             Amount                           per-                                                                             Pressure CO con- Hydro-                                                                            Distribution of hydrocarbons                                                                   of  of                  Catalyst     ature                                                                            (kg/ GHSV                                                                              version                                                                            CO.sub.2                                                                         carbon                                                                            formed (wt %)    C.sub.2.sup.=                                                                     C.sub.2 to                                                                    C.sub.4             Composition  (°C.)                                                                     cm.sup.2 G)                                                                        (hr .sup.-1)                                                                      (%)  (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                          C.sub.4                                                                         C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                     formed              __________________________________________________________________________    Example 5:                                                                    (19)                                                                             2% Ru--2.2% K--                                                                         400                                                                              0    1200                                                                              15.0 12.5                                                                             87.5                                                                              18.1                                                                             46.4                                                                             24.9                                                                             7.3                                                                             2.9                                                                             0.4                                                                             0 51.56                                                                             78.6                   0.45% S/γ-MnO.sub.2                                                  (20)                                                                             2% Ru--2.1% K--                                                                         400                                                                              0    1200                                                                              13.5 18.3                                                                             81.7                                                                              18.8                                                                             40.7                                                                             23.3                                                                             7.8                                                                             5.0                                                                             2.8                                                                             1.6                                                                             44.1                                                                              71.8                   0.45% S/γ-MnO.sub. 2                                                 __________________________________________________________________________

EXAMPLE 6 AND COMPARATIVE EXAMPLE 5

A Ru-Na/MnO₂ catalyst (22) was prepared using commercially availableamorphous MnO₂ (guaranteed reagent, surface area 150.9 m² /g) by thesame manner as that for the catalyst (1) shown in Example 1 except thataddition of sulfur by processing with an aqueous solution of H₂ SO₄ wasnot carried out, and the reaction was conducted using it. After thereaction was carried out under the prescribed reaction conditions, 5 mlportions of H₂ S gas were injected 9 times into a reaction gas by apulse injection process so that a part of the surface of the catalystwas poisoned. Using this catalyst (21), the reaction was carried out.Results are shown in Table 6. Incorporation of sulfur on the catalystcan be carried out by various processes. Conversion, distribution of theproduct, and olefin selectivity were nearly equal in the case of usingthe catalyst (21) of this example obtained by directly introducing agaseous sulfur compound together with the reaction gas and in the caseof using the catalysts obtained by introducing a sulfur component as asulfuric acid radical or SCN ion, etc., at preparation of the catalyst(refer to Examples 1 to 5). Accordingly, the process which comprisesintroducing a gaseous sulfur compound into a reaction system, as shownin this example, is a simple process in the viewpoint of preparation ofthe catalyst. As is shown in Table 6, selectivity for C₂ to C₄ lowerolefins, and particularly the ratio of olefin/paraffin in the C₂fraction are remarkably improved in case of using the catalyst (21) ofthe present invention as compared with the case of using the catalyst(22) to which H₂ S was not added.

Further, it should be noticed that the catalyst of the present inventionhas excellent sulfur resistance and olefin selectivity was improved bythe sulfurization processing according to the present invention ascompared with the Ru/γ-Al₂ O₃ catalyst (24) in comparative example. Thecatalyst (23) was prepared by sulfurizing the catalyst (24) with 5 mlportions of H₂ S gas 4 times, i.e., for a total of 20 ml. When thecatalyst (23) used, CO conversion deteriorated.

                                      TABLE 6                                     __________________________________________________________________________                  Reaction conditions                                                           Tem-                                                                             Pres-   CO  Selectivity              Ratio                                                                             Amount                            per-                                                                             sure    con-   Hydro-                                                                            Distribution of hydrocarbons                                                                    ofrmed                                                                            of                  Catalyst      ature                                                                            (kg/                                                                              GHSV                                                                              version                                                                           CO.sub.2                                                                         carbon                                                                            (wt %)            C.sub.2.sup.=                                                                     C.sub.2 to                                                                    C.sub.4             Composition   (°C.)                                                                     cm.sup.2 G)                                                                       (hr.sup. -1)                                                                      (%) (%)                                                                              (%) C.sub.1                                                                          C.sub.2                                                                          C.sub.3                                                                           C.sub.4                                                                         C.sub.5                                                                         C.sub.6                                                                         C.sub.7                                                                         C.sub.2.sup.-                                                                     formed              __________________________________________________________________________    Example 6:                                                                    (21)                                                                             1% Ru--0.28% Na--                                                                        400                                                                              0   150 34.8                                                                              25.6                                                                             74.4                                                                              20.3                                                                             45.6                                                                             24.3                                                                              6.0                                                                             2.6                                                                             1.1                                                                             0.1                                                                             16.51                                                                             75.9                   0.37% S/MnO.sub.2                                                          Comparative Example 5:                                                        (22)                                                                             1% Ru--0.28% Na/                                                                         400                                                                              0   150 35.6                                                                              17.7                                                                             82.2                                                                              30.0                                                                             39.7                                                                             22.4                                                                              5.6                                                                             1.3                                                                             0.9                                                                             0.1                                                                             0.49                                                                              67.7                   MnO.sub.2                                                                  (23)                                                                             1% Rn--0.21% S/                                                                          400                                                                              0   150  2.4                                                                               1.8                                                                             98.2                                                                              70.5                                                                             24.3                                                                             3.4 1.2                                                                             0.5                                                                             0.1                                                                             0 2.48                                                                              28.9                   γ-Al.sub.2 O.sub.3                                                   (24)                                                                             1% Ru/γ-Al.sub.2 O.sub.3                                                           400                                                                              0   150 42.1                                                                               2.1                                                                             97.9                                                                              99.9                                                                             0.02                                                                             0.007                                                                             0 0 0 0 0   0.03                __________________________________________________________________________

EXAMPLE 7 AND COMPARATIVE EXAMPLE 6

γ-type MnO₂ prepared according to the process shown in Reference Example1 (surface area 223.1 m² /g) was immersed in 80 ml of an aqueoussolution of sulfuric acid having pH 5.2, and it was stirred at roomtemperature for 25 hours. After it was filtered and dried, it wasimmersed in water (80 ml), and a concentrated aqueous solution of NaOHwas added dropwise thereto to adjust the pH to 8.5. The resultingNa-S/γ-MnO₂ mixture was processed with a solution of ruthenium chloridein a mixture of water-ethanol in equal volumes so as to support 1 wt %as the metal per the catalyst weight. After the solvent was removed anddrying was carried out in an oven, the product was subjected tocalcining processing in the air by means of an electric oven at 450° C.for 24 hours to produce a catalyst (25). This catalyst was placed in areactor and subjected to reduction processing in the same manner as inExample 1, and the reaction was carried out using it. Reactionconditions and distribution and composition of the product are shown inTable 7. When the catalyst was subjected to calcining processing in airafter application of ruthenium, distribution of the product greatlychanged, whereby it became advantageous for forming a high boiling pointfraction, as compared with the case of the catalyst (5) in Example 2.Further, though the distribution of the product followed theSchultz-Flory law, the ratio of olefin/paraffin in the product was high,as compared with the case of using the Ru/γ-Al₂ O₃ catalyst (26) (whichwas calcined at 450° C. for 24 hours) shown as a comparative example.Further, it was understood that α-olefin content in the olefincomposition obtained was 90% or more and the catalyst was advantageousin olefin selectivity, particularly with respect to formation of higherα-olefins, at high temperature under high pressure.

                                      TABLE 7                                     __________________________________________________________________________                 Reaction conditions  Selectivity                                              Temper-         CO con- Hydro-                                                                            Distribution of hydro-               Catalyst     ature                                                                              Pressure                                                                            GHSV version                                                                            CO.sub.2                                                                         carbon                                                                            carbons formed (wt %)                Composition  (°C.)                                                                       (kg/cm.sup.2 G)                                                                     (hr.sup.-1)                                                                        (%)  (%)                                                                              (%) C.sub.1                                                                           C.sub.2                                                                          C.sub.3                                                                          C.sub.4                    __________________________________________________________________________    Example 7:                                                                    (25) 1% Ru--0.48% Na--                                                                     330  10    1200 46.7 8.3                                                                              91.7                                                                              11.7                                                                              12.4                                                                             17.5                                                                             14.4                       0.29% S/γ-MnO.sub.2                                                     (Ratio of olefin/paraffin)                   2.02                                                                             5.06                                                                             4.81                       Comparative Example 6:                                                        (26) 1% Ru/γ-Al.sub.2 O.sub.3                                                        330  10    1200 48.5 2.7                                                                              97.3                                                                              68.9                                                                              13.0                                                                             11.8                                                                             3.9                        (Ratio of olefin/paraffin)                   0.02                                                                             0.3                                                                              0.19                       __________________________________________________________________________    Catalyst     Distribution of hydrocarbons formed (wt %)                       Composition  C.sub.5                                                                          C.sub.6                                                                          C.sub.7                                                                          C.sub.8                                                                          C.sub.9                                                                          C.sub.10                                                                         C.sub.11                                                                         C.sub.12                                                                         C.sub.13                                                                         C.sub.14                                                                         C.sub. 15                                                                        C.sub.16                                                                         C.sub.17                                                                         C.sub.18                  __________________________________________________________________________    Example 7:                                                                    (25) 1% Ru--0.48% Na--                                                                     11.9                                                                             6.9                                                                              4.8                                                                              4.6                                                                              2.9                                                                              2.6                                                                              1.8                                                                              1.6                                                                              1.5                                                                              1.4                                                                              1.2                                                                              1.0                                                                              0.8                                                                              1.0                       0.29% S/γ-MnO.sub.2                                                     (Ratio of olefin/paraffin)                                                                 4.66                                                                             4.31                                                                             4.14                                                                             3.97                                                                             3.63                                                                             3.42                                                                             3.19                                                                             2.73                                                                             2.15                                                                             1.54                                                                             1.08                                                                             0.62                                                                             0.42                         Comparative Example 6:                                                        (26) 1% Ru/γ-Al.sub.2 O.sub.3                                                        1.5                                                                              0.6                                                                              0.2                                                                              0.1                                                                              0  0  0  0  0  0  0  0  0  0                         (Ratio of olefin/paraffin)                                                                 0.15                                                                             0.10                                                                             0.04                                                                             0.02                                                    __________________________________________________________________________     Note:                                                                         C.sub.18+  means the amount of C.sub.18 and higher hydrocarbons formed.  

As shown in the above described Examples 1 to 7, according to thepresent invention, hydrocarbons rich in olefins are obtained from asynthesis gas in good selectivity and yield when a carbon monoxidereduction catalyst comprising ruthenium, manganese oxide, alkali metal,and sulfur as components is used.

EXAMPLE 8 AND COMPARATIVE EXAMPLE 7

Preparation of carbon monoxide reduction catalyst:

A carbon monoxide reduction catalyst comprising ruthenium, manganeseoxide, alkali metal, and sulfur components was prepared as follows.

Manganese oxide obtained in Reference Example 1 was ground by means ofan agate mortar to produce a fine powder. After it was immersed in anaqueous solution of sulfuric acid so that the sulfur content became 0.5wt % based on the whole weight of the carbon monoxide reductioncatalyst, it was dried at 110° C. for 3 hours. After it was immersedagain in an aqueous solution of potassium hydroxide so that thepotassium content became 1.35 wt % based on the total weight of thecarbon monoxide reduction catalyst, it was dried at 110° C. for 3 hours,and it was subjected to calcining processing at 450° C. for 3 hours toprepare a mixture composed of manganese oxide, alkali metal, and sulfurcomponents. After this mixture was immersed in an aqueous solution ofruthenium chloride so that the ruthenium content became 2.0 wt % basedon the total weight of the carbon monoxide reduction catalyst, it wasdried at 120° C. for 3 hours, and subsequently calcined at 450° C. for 8hours to obtain a carbon monoxide reduction catalyst A (abbreviation for2% Ru-1.35% K-0.5% S/MnO₂).

Preparation of crystalline zeolite:

ZSM-5 type zeolite was synthesized as follows.

Solution A, wherein 17.1 g of aluminium sulfate, 18.5 g of concentratedsulfuric acid and 22.6 g of tetrapropylammonium bromide were dissolvedin 180 g of water, Solution B, wherein 207 g of water glass No. 3(silica 28.9%) was dissolved in 140 g of water, and Solution C wherein78.8 g of sodium chloride was dissolved in 320 g of water were prepared.Solution C was vigorously stirred and Solution A and Solution B wereadded dropwise at the same time and mixed. Then, the mixture was put ina 1 l stainless steel autoclave. It was stirred at 100-150 rpm, and thetemperature was gradually raised. The reaction was carried out at 160°C. for 20 hours. Thereafter, the reaction mixture was cooled slowly. Theresulting fine white crystals were filtered off and washed with water.This operation was repeatedly carried out until the pH of washing waterbecame about 8. After dried at 120° C., it was calcined in air at 550°C. for 6 hours. In order to convert into H-type zeolite, ion-exchangewas carried out at a temperature of 80° to 90° C. using a 2N aqueoussolution of ammonium chloride in an amount of 5 ml per gram of zeolite.After filtered off and washed with water, the same processing wasrepeatedly carried out 5 times using a fresh aqueous solution ofammonium chloride. Thereafter, it was washed with water and dried at120° C. for 3 hours. It was then calcined again in air at 550° C. for 6hours to obtain H-type ZSM-5 type zeolite.

Catalyst of the present example:

Equal volumes of the above described carbon monoxide reduction catalystA and the above described H-type ZSM-5 zeolite were sufficiently mixedin a mortar, and the mixture was then molded in the size of 1 to 2 mm toobtain a catalyst (27) (ruthenium 1.6 wt %, potassium 1.0 wt % andsulfur 0.4 wt %, based on the whole weight of the catalyst;abbreviation: 1.6% Ru-1.0% K-0.4% S/MnO₂ +ZSM-5).

Comparative catalyst:

A carbon monoxide reduction catalyst which was composed of ruthenium,manganese oxide, and alkali metal component, that which was composed ofruthenium, manganese oxide, and sulfur component and that which wascomposed of ruthenium, and manganese oxide component were prepared,respectively, in the same manner as that for preparing the abovedescribed carbon monoxide reduction catalyst A, except that processingwith an aqueous solution of sulfuric acid, processing with an aqueoussolution of potassium hydroxide and processing with aqueous solutions ofboth sulfuric acid and potassium hydroxide were not carried out,respectively. Then, catalysts (28), (29) and (30) were prepared,respectively, using zeolite in the same ratio of mixing by the samemanner as those for the catalyst (27).

Further, a carbon monoxide reduction catalyst (31) composed ofrethenium, and manganese oxide component which was not mixed withzeolite was prepared.

Reaction:

The prepared catalyst was placed in a reactor. After it was previouslyreduced with hydrogen at 400° C. for 2 hours, the reaction was carriedout using a synthesis gas composed of carbon monoxide and hydrogen (H₂/CO=1) and results shown in Table 8 were obtained. The amount of thecatalyst charged was 4 ml (3.39 g) in case of catalysts (27), (28),(29), and (30) and 2 ml in case of the catalyst (31).

In the case of using the catalyst (27) prepared by mixing the carbonmonoxide reduction catalyst composed of ruthenium, manganese oxide,alkali metal, and sulfur component and H-ZSM-5 type zeolite, the amountof methane formed was sufficiently small, formation of the gasolinefraction of C₅ to C₁₂ hydrocarbons was remarkably improved, and thearomatic component content in the formed hydrocarbons was high, ascompared with the case of using catalysts which were lacking in eitherthe alkali metal or sulfur component, or both of them. Further, itshould be particularly noted that since the methane formation rate islow in a wide temperature range, a gasoline fraction having high qualitycan be obtained in a high yield.

                                      TABLE 8                                     __________________________________________________________________________                  Reaction conditions Selectivity            Aromatic                           Temper-        CO con- Hydro-                                                                            Distribution of                                                                               componenton          Catalyst      ature                                                                              Pressure                                                                            GHSV                                                                              version                                                                            CO.sub.2                                                                         carbon                                                                            product (wt %)  content              Composition   (°C.)                                                                       (kg/cm.sup.2 G)                                                                     (hr.sup.-1)                                                                       (%)  (%)                                                                              (%) C.sub.1                                                                          C.sub.2 to C.sub.4                                                                 C.sub.5 to                                                                         C.sub.13+                                                                        (wt                  __________________________________________________________________________                                                             %)                   Example 8:                                                                    (27)                                                                             1.6% Ru--1.0% K--                                                                        300  10.3  600 47.6 0.8                                                                              99.2                                                                               5.7                                                                              9.7 83.3 1.3                                                                              28.9                    0.4% S/γ-                                                               MnO.sub.2 + ZSM-5                                                          (27)                                                                             1.6% Ru--1.0% K--                                                                        270  10.0  600 35.6 0.8                                                                              99.2                                                                               4.5                                                                             15.3 79.4 0.8                                                                              18.5                    0.4% S/γ-                                                               MnO.sub.2 + ZSM-5                                                          (27)                                                                             1.6% Ru--1.0% K--                                                                        330  10.0  600 62.1 21.0                                                                             79.0                                                                              10.1                                                                             25.0 64.6 0.3                                                                              27.7                    0.4% S/γ-                                                               MnO.sub.2  + ZSM-5                                                         Comparative Example 7:                                                        (28)                                                                             1.6% Ru--1.0% K/                                                                         300  10.1  600 48.2 1.5                                                                              98.5                                                                              18.7                                                                             47.4 32.4 1.5                                                                              12.3                    γ-MnO.sub.2 + ZSM-5                                                  (29)                                                                             1.6% Ru--0.4% S/                                                                         300  10.2  600 48.0 1.2                                                                              98.8                                                                              24.5                                                                             38.3 35.8 1.4                                                                              10.1                    γ-MnO.sub.2 + ZSM-5                                                  (30)                                                                             1.6% Ru/γ-                                                                         300  10.0  600 50.8 2.1                                                                              97.9                                                                              20.7                                                                             45.4 32.9 1.0                                                                              11.7                    MnO.sub.2 + ZSM-5                                                          (31)                                                                             2.0% Ru/γ-MnO.sub.2                                                                300  10.5  1200                                                                              49.3 1.8                                                                              98.2                                                                              13.1                                                                             42.2 36.2 8.5                                                                               0.0                 __________________________________________________________________________     Note:                                                                         Aromatic component content means the content in hydrocarbons formed.          Hereinafter, it shows the same meaning.                                  

EXAMPLE 9

A catalyst (32) was prepared in the same manner as that for preparingthe catalyst (27) in Example 8 except that calcining was not carried outin case of preparing the carbon monoxide reduction catalyst A used forthe catalyst (27). After it was reduced with hydrogen at 400° C., asynthesis gas of a ratio H₂ /CO of 0.5/1 (molar ratio) was allowed topass through the catalyst charged in an amount of 4 ml to carry out thereaction, and the results shown in Table 9 were obtained.

EXAMPLE 10

Crystalline iron silicate and crystalline gallium silicate were preparedin the same manner as that for preparing the zeolite catalyst of thecatalyst (27), except that 5.10 g of ferric chloride (FeCl₃. 6H₂ O) and8.10 g of gallium sulfate, respectively, were used, instead of the 17.1g of aluminium sulfate in the case of preparing the crystalline zeolitefor incorporating in the catalyst (27) in Example 8, As Y-type zeolitecommercially available SK-41 produced by Union Carbide Co. was used.These crystalline zeolite catalysts were mixed with the same carbonmonoxide reduction catalyst A as that for incorporating in the catalyst(27) in Example 8, in equal volumes, to prepare catalysts (33), (34),and (35), respectively. Using these catalysts, the reaction was carriedout similarly to Example 8. The results are shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________                  Reaction conditions Selectivity            Aromatic                           Temper-        CO con- Hydro-                                                                            Distribution of                                                                               componenton          Catalyst      ature                                                                              Pressure                                                                            GHSV                                                                              version                                                                            Co.sub.2                                                                         carbon                                                                            product (wt %)  content              Composition   (°C.)                                                                       (kg/cm.sup.2 G)                                                                     (hr.sup.-1)                                                                       (%)  (%)                                                                              (%) C.sub.1                                                                          C.sub.2 to C.sub.4                                                                 C.sub.5 to                                                                         C.sub.13+                                                                        (wt                  __________________________________________________________________________                                                             %)                   (32)                                                                             1.6% Ru--1.0% K--                                                                        360   4.7  300 34.2 4.0                                                                              96.0                                                                              16.2                                                                             16.3 67.5 0  31.1                    0.4% S/MnO.sub.2 +                                                            ZSM-5                                                                      Example 10:                                                                   (33)                                                                             1.6% Ru--1.0% K--                                                                        300   10.0 600 47.3 0.9                                                                              99.1                                                                              6.9                                                                              12.2 80.3 0.6                                                                              20.2                    0.4% S/γ-MnO.sub.2 +                                                    Fe silicate                                                                (34)                                                                             1.6% Ru--1.0% K--                                                                        300  10.0  600 48.2 1.5                                                                              98.5                                                                              7.0                                                                              11.5 80.9 0.6                                                                              20.4                    0.4% S/γ-MnO.sub.2 +                                                    Ga silicate                                                                (35)                                                                             1.6% Ru--1.0% K--                                                                        300  10.0  600 47.7 1.8                                                                              98.2                                                                              8.3                                                                              25.3 65.2 1.2                                                                              12.6                    0.4% S/γ-MnO.sub.2 +                                                    SK-41                                                                      __________________________________________________________________________

As be shown in Examples 8 to 10, when catalysts obtained by mixing thecarbon monoxide reduction catalyst composed of ruthenium, manganeseoxide, alkali metal and sulfur component with zeolite in the presentinvention are used, hydrocarbons rich in a fraction capable of beingutilized as gasoline can be obtained directly from the synthesis gas ina high yield.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for producing hydrocarbons whichcomprises bringing a gas mixture comprising hydrogen and carbon monoxideinto contact with a catalyst comprising at least 5% by weight based onthe total catalyst a carbon monoxide reduction catalyst at reactionconditions comprising a pressure of from 0 to 100 kg/cm² G and atemperature of from 100° to 500° C. to produce hydrocarbons, whereinsaid carbon monoxide reduction catalyst comprises 10 to 99.8 wt %manganese oxide, 0.01 to 8 wt % alkali metal, 0.001 to 3 wt % sulfur,and 0.1 to 50 wt % ruthenium based on the total weight of the carbonmonoxide reduction catalyst.
 2. A process according to claim 1, whereinthe catalyst consists essentially of said carbon monoxide reductioncatalyst.
 3. A process according to claim 1, wherein the catalystfurther comprises crystalline zeolite.
 4. A process according to claim1, wherein the carbon monoxide reduction catalyst additionally containsat least one of a member selected from the group consisting of TiO₂,SiO₂, Al₂ O₃, Cr₂ O₃, V₂ O₅, WO₃, MoO₃ and natural clay minerals.
 5. Aprocess according to claim 1 wherein the manganese oxide is at least oneoxide selected from the group consisting of MnO₂, Mn₂ O₃, MnO₃ O₄, andMnO.
 6. A process according to claim 1, wherein said alkali metal islithium, sodium, potassium, cesium, or rubidium.
 7. A process accordingto claim 3, wherein the crystalline zeolite is crystallinealuminosilicate or crystalline silicate.
 8. A process according to claim1, wherein the reaction conditions comprise a molar ratio of hydrogen tocarbon monoxide of from 0.1/1 to 10/1.
 9. A process according to claim1, wherein the carbon monoxide reduction catalyst contains from 0.05 to6 wt % alkali metal, from 0.07 to 1.5 wt % sulfur, and from 0.1 to 30 wt% ruthenium.
 10. A process according to claim 2, wherein the carbonmonoxide reduction catalyst contains from 0.05 to 6 wt % alkali metal,from 0.07 to 1.5 wt % sulfur, and from 0.1 to 30 wt % ruthenium.
 11. Aprocess according to claim 3, wherein the carbon monoxide reductioncatalyst contains from 0.05 to 6 wt % alkali metal, from 0.07 to 1.5 wt% sulfur, and from 0.1 to 30 wt % ruthenium.
 12. A process according toclaim 11, wherein the carbon monoxide reduction catalyst contains from0.5 to 25 wt % ruthenium.
 13. A process according to claim 1, whereinthe reaction conditions comprise a pressure of from 0 to 30 kg/cm² G, atemperature of from about 200° to 450° C., and a molar ratio of hydrogento carbon monoxide of from 0.5/1 to 4/1.
 14. A process according toclaim 2, wherein the reaction conditions comprise a pressure of from 0to 30 kg/cm² G, a temperature of from about 200° to 450° C., and a molarratio of hydrogen to carbon monoxide of from 0.5/1 to 4/1.
 15. A processaccording to claim 3, wherein the reaction conditions comprise apressure of from 0 to 30 kg/cm² G, a temperature of from about 200° to450° C., and a molar ratio of hydrogen to carbon monoxide of from 0.5/1to 4/1.
 16. A process according to claim 1, wherein the reactionconditions comprise a pressure of from 0 to 20 kg/cm² G, a temperatureof from about 250° to 400° C., and a molar ratio of hydrogen to carbonmonoxide of from 0.5/1 to 1/1.
 17. A process according to claim 1,wherein the carbon monoxide reduction catalyst additionally contains atleast one activator selected from the group consisting of magnesium,zinc, copper and iron.